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Driven by dataInfluence of chlorine substitution on the hydrolytic stability of biaryl ether nucleoside adducts produced by phenolic toxins.
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2013 Jul 19;78(14):7176-85. doi: 10.1021/jo401122j. Epub
2013 Jul 2.Influence of chlorine substitution on the hydrolytic stability of biaryl ether nucleoside adducts produced by phenolic toxins.1, , , , , , .1Department of Chemistry, University of Guelph, Guelph, Ontario, N1G 2W1, Canada.AbstractA kinetic study is reported for the acid-catalyzed hydrolysis of oxygen (O)-linked biaryl ether 8-2'-deoxyguanosine (dG) adducts produced by phenolic toxins following metabolism into phenoxyl radical intermediates. Strikingly, the reaction rate of hydrolysis at pH 1 decreases as electron-withdrawing chlorine (Cl) substituents are added to the phenoxyl ring. The Hammett plot for hydrolysis at pH 1 shows a linear negative slope with ρX = -0.65, implying that increased Cl-substitution diminishes the rate of hydrolysis by lowering N(7) basicity. Spectrophotometric titration provided an N(7)H(+) pKa value of 1.1 for the unsubstituted adduct 8-phenoxy-dG (Ph-O-dG). Model pyridine compounds suggest N(7)H(+) pKa values of 0.92 and 0.37 for 4-Cl-Ph-O-dG and 2,6-dichloro-Ph-O-dG (DCP-O-dG), respectively. Density functional theory (DFT) calculations also highlight the ability of the 8-phenoxy substituent to lower N(7) basicity and predict a preference for N(3)-protonation for highly chlorinated O-linked 8-dG adducts in water. The calculations also provide a rationale for the hydrolytic reactivity of O-linked 8-dG adducts in the gas-phase, as determined using electrospray mass spectrometry (ESI-MS). The inclusion of our data now establishes that the order of hydrolytic reactivity at neutral pH for bulky 8-dG adducts is N-linked & C-linked & O-linked, which correlates with their relative ease of N(7)-protonation.PMID:
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External link. Please review our .Radiation to personnel from activities induced in tank armor for enhanced-radiation and fission nuclear weapons
On the nuclear battlefield, the armored-force commander must know the possible hazard to personnel who replace original crews that have been incapacitated by the very short initial prompt dose from neutrons and neutron induced gamma rays. After the initial prompt dose, the initial prompt neutrons will activate the chrome-nickel steel armor of the tank at t = 0/sup +/, and the neutron-activated steel will have a time-dependent emission rate of gamma rays that will impinge on the tank crew. We evaluate this time-dependent dose on the replacement crew from induced activity for both a pure 1-kt fusion and a 1-kt fission nuclear weapon.Do you want to read the rest of this article?Request full-text
This research doesn't cite any other publications.ArticleIn the last five years, a flood of literature, both in the US and abroad, has pointed out the pros and cons of effects from enhanced-radiation (ER) and fission warheads. While these publications often focus on numerical differences that can be quite large, they seldom tell the reader how the numerical values were obtained. In this report, we assume pure-fusion, 50/50 fusion/fission, and... [Show full abstract]ArticleSeptember 1981Neutrons and photons resulting from the interaction of galactic cosmic rays with the material of an orbiting satellite or an orbiting space station at an altitude of some few hundreds of kilometers, and below the level of the radiation belts, were calculated as a function of geomagnetic latitude and solar activity level. The photon and neutron leakage currents from the top of the atmosphere... [Show full abstract]ArticleJuly 1972 · The time-dependent escape of neutrons and gamma rays from a nuclear explosion is of interest in Plowshare and nuclear weapons effects investigations, particularly with regard to generation of the electromagnetic pulse (EMP). In the present paper the neutron and gamma-ray leakage rates, spectra, and useful yield-related integral quantities are calculated for the 24kt S-device. EMP parameters... [Show full abstract]Article}

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